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Kinetics and mechanism of the thermal decomposition reaction of acetone cyclic diperoxide in the gas phase

✍ Scribed by Lázaro F. R. Cafferata; José D. Lombardo

Publisher
John Wiley and Sons
Year
1994
Tongue
English
Weight
376 KB
Volume
26
Category
Article
ISSN
0538-8066

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✦ Synopsis

Abstract

The kinetics of the thermal decomposition reaction of gaseous 3,3,6,6‐tetramethyl‐1,2,4,5‐tetroxane (ACDP) in the presence of n‐octane was studied in the 403.2–523.2 K temperature range. This reaction yields acetone as the organic product. Under optimum conditions, first‐order kinetics were observed, included when the S/V ratio of the Pyrex reaction vessel was increased by a nearly six‐fold factor. In the range 443.2–488.2 K the temperature dependence of the rate constants for the unimolecular reaction in conditioned vessels is given by In k~1~/(s^−1^) = (31.8 ± 2.5) − [(39.0 ± 2.5)/RT]. The value of the energy of activation in kcal/mol correspond to one OO bond homolysis of the ACDP molecule in a stepwise biradical initiated decomposition mechanism. At the lower reaction temperatures as well in preliminary experiments participation of a surface catalyzed ACDP decomposition process could be detected. © 1994 John Wiley & Sons, Inc.

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